Water reducible phenolic modified alkyd resin

ABSTRACT

Water reducible phenolic modified resins are described for use as binders in coating compositions which are non-lifting, recoatable with improved metal adhesion and corrosion resistance.

This is a division of application Ser. No. 781,096, filed Sept. 27,1985, now U.S. Pat. No. 4,649,173 issued 3-10-87.

The invention is directed to a new and improved water reducible phenolicmodified alkyd resin for use as a binder in coating compositions. Morespecifically, this invention relates to an alkyd coating resin which isa water reducible alkyd resin for use as a binder in a coatingcomposition which alkyd resin is modified by an alkylated phenolicresin, the modified alkyd resin being a water reducible binder whichprovides a non-lifting recoatable coating composition.

Environmental concern has become increasingly important in recent years.This concern not only extends to preservation of the environment for itsown sake, but extends to safety for the public as to both living andworking conditions. Volatile organic emissions resulting from coatingcompositions which are applied and used by industry and by the consumingpublic are often not only unpleasant, but contribute to photochemicalsmog. Fire and health hazards of organic solvents also are well known.Governments may or have established regulations setting forth guidelinesrelating to volatile organic compounds (VOCs) which may be released tothe atmoshpere. The United States Environmental Protection Agency (EPA)has established guidelines relating to the amount of VOCs released tothe atmosphere, such guidelines being scheduled for adoption by thestates of the United States. Guidelines relating to VOCs, such as thoseof the EPA, and environmental concerns are particularly pertinent to thepaint and industrial coating industry which uses organic solvents whichare emitted into the atmosphere.

With respect to coating compositions, and in response to environmentalconcern, organic coating resings, and most particularly alkyd coatingresins have been developed and are known to reduce organic emissionswith the use of water or an organic solvent water combination in lieu ofusing volatile organic solvents without water.

Moving from organic solvents to water or a water organic solventcombination not only changes the constituents of the alkyd, butfrequently changes the curing and/or solvent retention characteristicsof the coating compositions which contain the alkyd coating resin orbinder. Often water as a solvent in these coating compositions willlengthen the drying times of films of these coating compositions.Generally air-drying alkyd films on metal will blister such films ifthey are recoated within about a three day period. This is thought to becaused by solvent penetration into the base coat and probably relates toincomplete cure or a fast cure on the surface of the coat and/or solventretention in the base coat. Where second and third coats are requiredthere is an obvious efficiency advantage in being able to add theseadditional coats of coating composition as soon as possible afterapplying the base coat.

In conventional organic solvent alkyd coating resin systems, theincorporation of certain phenol-formaldehyde resins into the binderresin is known to help alleviate blistering in coating compositions.These organic solvent systems, however, do not use a trifunctional acidor anhydride such as trimelletic anhydride to achieve water solubility.In water reducible alkyd systems, however, such a component generally isneeded to partially react with the alkyd with residual reactive groupsforming salts permitting water solubility. As is known, a waterreducible alkyd resin is dispersed in water by mixing the resin with anamine or ammonia to form a salt which is then solubilized in water. Theuse of phenolic resins to minimize lifting with water reducible alkydbinders has heretofore been unknown.

Phenolic resins have been used with water soluble or reducible alkydcoating resins. These resins or binders, however, have required aminecross-linking agents, forced cures, and large amounts of tricarboxylicacids when formulated into coating compositions. Moreover, theliterature relating to such compositions has not suggested that the useof phenolic coating resins will alleviate or have any effect on therecoatability or blistering proclivities of water reducible alkydcoating resins.

U.S. Pat. No. 4,347,335 to Thomas describes a water reducible polyesterresin modified with a phenolic resin, which modified resin the patentstates provides coatings with good thermal ratings, bond strengths and acoating composition with a good shelf life. The coating compositions andbinders described in Thomas, however, require forced cures, aminoplastcross-linking agents, and substantial amounts of tricarboxylic acids.Moreover, the recoatability of the coating composition and blisteringproblem inherent with coating compositions with alkyd coating resins isnot recognized or even discussed.

U.S. Pat. No. 4,196,109 to Laganis et al. describes an alkyd resinmodified with a phenolic resin with carboxyl substituents and a triazinederivative in combination with water and organic solvent. The coatingcompositions of Laganis et al., however, require aminoplastcross-linkers and use forced cures. Recoatability and blistering are notdiscussed.

It has been found that by incorporating an alkylated phenolic resin intoa water reducible alkyd resin in an amount from about 4 to about 20percent by weight based upon the total weight of the phenolic modifiedalkyd resin, an alkyd coating resin which provides a non-liftingrecoatable coating composition is obtained. Moreover, the coatingcompositions of the invention are curable by oxidative cross-linking andhave improved metal adhesion and corrision resistance.

As used herein alkyd resin generally means a condensation productinvolving a polybasic acid with a polyhydric alcohol with the additionof modifying agents such as higher fatty acids. As used herein, phenolicresin generally means a phenol-formadehyde resin which is the reactionproduct of formaldehyde with a hydroxy substituted aromatic ringincluding phenol which ring has one or more hydroxyl groups on it.

In respect to the invention described herein, the alkyd resin used inthe composition of the invention is the esterification product ofdibasic acids with polyols, monobasic carboxylic acids or vegetable oilprecursers thereof including saturated and unsaturated fatty acidshaving between 10 and 22 carbon atoms and monobasic aromatic acids, anda tricarboxylic acid or anhydride thereof. Esterification catalystsgenerally are used in preparing the alkyd. Aromatic dicarboxylic acidsthat can be used to prepare the alkyd resin are isophthalic acid,terephthalic acid, and phthalic acid. Polyhydric alcohols that can beused to prepare alkyd resins may have two or more hydroxyl groups andinclude ethylene glycol, propylene glycol, 1,3-butylene glycol,pentanediol, neopentyl glycol, hexylene glycol, diethylene glycol,dipropylene glycol, triethylene glycol, glycerol, trimethylolethane,trimethylol propane, pentaerythritol, methylglucoside,dipentaerythritol, and sorbitol with neopentyl glycol, trimethyol ethaneand trimethylol propane being preferred. Tricarboxylic acids or theiranhydrides that can be used to prepare the alkyd resin are trimelleticacid, trimelletic anhydride, trimesic acid and the like with trimelleticanhydride being preferred. Fatty or other carboxylic acids that are usedto prepare alkyd resins are capric acid, linoleic acid, benzoic acid,dehydrated castor oil fatty acids, heat-bodied soya oil fatty acids,tung oil fatty acids, linseed oil fatty acids, safflower oil fattyacids, soya oil fatty acids, tall oil fatty acids and the like.Esterification catalysts that are used in the process for preparingalkyd resins are butyl stannoic acid, barium oxide, barium hydroxide,barium naphthenate, calcium oxide, calcium hydroxide, calciumnaphthenate, lead oxide, lithium hydroxide, lithium naphthenate, lithiumrecinollate, sodium hydroxide, sodium naphthenate, zinc oxide, and leadtallate with butyl stannoic acid being preferred.

The phenolic modified alkyd coating resin of the invention is producedby adding the alkylated phenolic resin to the reaction mixture during orafter preparation of the alkyd, preferably after substantiallycompleting the esterification reaction between the dibasic acids andpolyols. The addition and reaction of the triacid, to the reactionproduct, however is after the esterification reaction and preparation ofthe alkyd.

In respect to the invention described herein, an alkylated phenolicresin is a reaction product of an alkylated phenol and formaldehydewherein the alkyl substitution is at the paraposition on the aromaticring which substitution is with straight or branched alkyl groups havingfrom 1 to 18 carbon atoms, preferably the alkylation being tertiarybutyl. The alkylated phenolic resin is non-heat reactive and made underacid conditions.

By using a non-heat reactive alkylated phenolic resin it would beexpected to obtain a product which is a simple physical blend ofalkylated phenolic resin and alkyd. While not intending to be bound byany theory, it appears that an interreaction between the alkyd andalkylated phenolic resin occurs to render an alkylated phenolic modifiedcoating resin which has improved recoatability characteristics whereinthe coating composition containing the coating resin is fast drying,non-lifting and does not require aminoplast cross-linking agents.Additional to improved recoatability, the coating resin of the inventionwithout amino cross-linking agents provides coating compositions withimproved corrosion resistance, improved early water resistace andimproved metal adhesion.

It is an object of the invention to provide a water reducible alkydcoating resin modified with an alkylated phenolic resin which willprovide a non-lifting, recoatable coating composition which is fastdrying and which may be free of aminoplasts or amino cross-linkingagents.

It is another object of the invention to provide a method of making anew alkylated phenolic resin modified alkyd which will provide anon-lifting, recoatable coating compositions.

These and other objects of the invention will become more apparent withreference to the following detailed description.

Generally the alkylated phenolic modified alkyd coating resin is made byfirst obtaining a first ester by reacting with heat from about 20 toabout 50 parts by weight polyol per 100 weight of the resulting alkydcoating resin of the invention (hereafter "parts by weight" unlessotherwise indicated) with from about 15 to about 60 parts by weightfatty acid and from about 0.005 to about 0.05 parts by weight of anesterification catalyst such as a butyl stannoic acid catalyst soldunder the name Fascat 4100 by M&T Chemicals, Inc. When the latterreaction mixture containing the first ester has an acid value of lessthan 15 and preferably less than 3, the reaction mixture is cooled andfrom about 15 to about 50 parts by weight of a dibasic acid or anhydridethereof is added thereof; the resulting reaction mixture being heated toform an intermediate polyester with an acid value of less than about 25and preferably between 11 to 12. The reaction mixture containing theintermediate polyester is cooled and the alkylated phenolic resin isadded thereto with agitation and heated to form an alkylated phenolicmodified polyester resin with an acid value of about 5 to about 35,preferably about 18. The alkylated phenolic modified polyester resin ismixed with heat with from about 3 to about 15 parts by weight of atricarboxylic acid of anhydride thereof which yields and alkylatedphenolic modified alkyd resin with an acid value of from about 30 toabout 60 and preferably about 35 to about 45. The prereaction of thepolyol is preferred. Further, the alkylated phenolic resin may be mixedwith the alkyd after the formation of the alkyd or with its prereactedcomponents with the addition after the formation of the alkyd beingpreferred. The trimelletic anhydride or its equivalent, however, must becharged after the formation of the alkyd. At 50% solids in xylene analkylated phenolic modified alkyd resin, according to the invention, canhave a viscosity in the range of S to U and preferably about T on theGardner-Holdt scale as measured by ASTM method D1545-76.

The modified alkyd resin may be thinned with from about 50 to about 80parts by weight of an organic solvent such as butoxyethanol, secondarybutanol, propoxypropanol, pent-oxone or 4 methoxy-4-methylpentanone-2,or diacetone alcohol. From about 5 to about 60 parts by weight (basedupon the weight of the coating composition) of the modified alkyd maythen be ground or dispersed with pigments, solvent and metal driers toprovide a coating composition with a pigment binding ratio of from about0.05 to about 1.5.

The following examples are provided to illustrate the invention morefully; however, they should not be construed as limiting the scope ofthe invention, many variations of which are contemplated.

EXAMPLE 1

24.12 parts by weight of a C₁₈ synthetic fatty acid derived from talloil (commercially available from Hercules Chemical Company as Pamolyn327-B) and 14.86 parts by weight trimethylol propane is charged into areaction vessel fitted with a distillation column under nitrogen andheated to 280° F. whereupon 0.01 parts by weight of a butyl stannoicacid esterification catalyst (Fascat 4100) is added to the reactionmixture which is heated to 360° F. where distillation begins. Thereaction mixture then is heated to 440° F. for over 11/2 hours with awater loss of about 1.52 parts by weight to attain an acid value lessthan 3. When the latter acid value is attained, the reaction is cooledto 325° F. and 8.01 parts by weight of neopentylglycol (1% excess),23.22 parts by weight isophthalic acid, 2.10 parts by weightterephthalic acid and 0.01 parts by weight Fascat 4100 are added to thecoooled reaction mixture which then is heated to about 390° F. at whichtemperature distillation resumes. From 390° F. the reaction mixture isheated to 440° F. for over 2 hours with the loss of 5.37 parts by weightwater and 0.08 parts by weight glycol, to attain an acid value of11.0-12.0 and a Gardner-Holdt viscosity of Y at 70% solids in xylene.After the reaction mixture has an acid value between 11.0-12.0 thereaction mixture is cooled rapidly to 410° F., the nitrogen reduced toblanket, agitation increased and 5.99 parts by weight of an oil solubletertiary butyl phenolic resin having a softening point of 235°-250° F.(available from Union Carbide Corporation as CK2500) is added to thereaction mixture. After the addition of the phenolic, the reactionmixture is held at 390°-400° F. for 1/2 hour with the phenolic beingdissolved. The reaction mixture with the dissolved phenolic then iscooled to 350°-355° F. and is sampled such that the reaction mixtureshould have an acid value of 15 to 20 and a Gardner-Holdt viscosity of Zat 70% solids in xylene. After the addition of the phenolic and the acidvalue of 18 is reached, 3.65 parts by weight of trimellitic anhydride isadded to the reaction mixture which is reacted at about 345°-350° F. for15 minutes to attain an acid value of 42, and a Gardner-Holdt viscosityof N at 50% solids in xylene. After the addition of the trimellitic andthe reaction mixture is sampled for an acid value of 42, heating iscontinued at 345°-350° F. which heat is held until the reaction mixtureis sampled for a Gardner-Holdt viscosity of Q-R at 50% xylol; at whichtime the heat is reduced to 330° F. which is held until the reactionmixture is sampled for a viscosity of T-T 1/2 at 50% xylol. After aviscosity of T-T 1/2 is reached, the resulting phenolic modified alkydis cooled to 300° F. and 12.50 parts by weight of 2-butoxyethanol isadded thereto with agitation. After addition of the 2-butoxyethanol,12.50 parts by weight of secondary butanol is added to the phenolicmodified alkyd resin, both the butyl cellosolve and secondary butanolbeing added to thin the alkyd for handling and drumming.

EXAMPLE 2

The same procedure of Example 1 with the following reactants.

    ______________________________________                                                               PARTS BY                                               REACTANT               WEIGHT                                                 ______________________________________                                        1.    C.sub.18 fatty acid (Pamolyn 200)                                                                  21.05                                              2.    Tall oil fatty acid with less                                                                      2.18                                                     than 1% by weight rosin acids                                                 (Pamak 1 from Hercules                                                        Chemical Company)                                                       3.    C.sub.18 saturated acid                                                                            0.66                                                     (Hydrolfol acid 1895                                                          from Ashland Chemical Co.)                                              4.    C.sub.16 saturated fatty                                                                           0.27                                                     acid (Hydrofol acid 1690                                                      from Ashland Chemical Company)                                          5.    Trimethylol propane  15.86                                              6.    Esterification catalyst                                                                            0.01                                                     (Fascat 4100)                                                                                      40.03                                                    Water (water loss)   1.52                                                                          38.51                                              7.    Neopentyl glycol (1% excess)                                                                       6.76                                               8.    Isophthalic acid     23.38                                              9.    Terephthalic acid    2.11                                               10.   Esterification catalyst                                                                            0.01                                                     (Fascat 4100)                                                                                      77.77                                                    Water                5.36                                                                          65.41                                                    Glycol loss          0.07                                                                          65.34                                              11.   Butylated phenolic   6.00                                                     resin (CK 2500)                                                                                    71.34                                              12.   Trimellitic anhydride                                                                              3.66                                                                          75.00                                              13.   2-butoxyethanol      12.50                                              14.   Secondary Butanol    12.50                                                                         100.00                                             ______________________________________                                    

Reactants 1-5 are charged and reacted as in Example 1 to an acid valueless than 3. The reaction mixture then is cooled to 325° F. andreactants 7 to 10 are added with the mixture being heated to 440° F. forover 2 hours, with the water and glycol loss as indicated, to an acidvalue of 8. After the latter acid value is obtained, the reactionmixture is cooled to 410° F. and reactant 11 is added and held attemperature for 30 minutes then cooled to 350° F. After cooling reactant12 is added under nitrogen blanket and the temperature held at 340°-345°F. for 15 minutes whereupon it is cooled to 310°-320° F. and held atthat temperature until a viscosity of V 1/2-W at 50% nonvolatiles inxylene is attained. Then the reaction is cooled to 200° F. and 13 isadded. With further cooling to 170° F.14 is added.

EXAMPLE 3

The following unmodified alkyd resin was prepared pursuant to theprocedures set forth in Examples 1 and 2.

    ______________________________________                                                               PARTS BY                                               REACTANT               WEIGHT                                                 ______________________________________                                        1.    C.sub.18 fatty acid (Pamolyn 200)                                                                  22.98                                              2.    Tall oil fatty acid with                                                                           2.38                                                     less than 1% by weight rosin                                                  acids (Pamak 1 from Hercules                                                  Chemical Company)                                                       3.    C.sub.18 saturated acid                                                                            0.72                                                     (Hydrolfol acid 1895                                                          from Ashland Chemical Co.)                                              4.    C.sub.16 saturated fatty acid                                                                      0.30                                                     (Hydrofol acid 1690                                                           from Ashland Chemical Company)                                          5.    Trimethylol propane  19.08                                              6.    Esterification catalyst                                                                            0.01                                                     (Fascat 4100)                                                                                      45.47                                                    Water (water loss)   1.66                                                                          43.81                                              7.    Neopentyl glycol (1% excess)                                                                       5.12                                               8.    Isophthalic acid     26.20                                              9.    Terephthalic acid    2.37                                               10.   Esterification catalyst                                                                            0.01                                                     (Fascat 4100)                                                                                      77.51                                                    Water (water loss)   6.12                                                                          71.39                                                    Glycol loss          0.05                                                                          71.34                                              11.   Trimellitic anhydride                                                                              3.66                                                                          75.00                                              12.   2-butoxyethanol      12.50                                              13.   Secondary Butanol    12.50                                                                         100.00                                             ______________________________________                                    

The acid value after reactants 7-10 are added is 16-17; thereafter thereaction is cooled to 350° F. and reactant 11 is added. The reactionthen is held at 345°-350° F. for 15 minutes, then cooled to 300° F. andheld at that temperature for a viscosity of X at 50% nonvolatiles inxylene. Then 12 and 13 are added while cooling the reaction to 170° F.

EXAMPLE 4

    ______________________________________                                                               PARTS BY                                               REACTANT               WEIGHT                                                 ______________________________________                                        1.    A refined tall fatty acid (Pamolyn                                                                 24.64                                                    327B Hercules)                                                          2.    Trimethylolpropane   12.52                                              3.    Neopentyl glycol     8.24                                               4.    Isophthalic acid     20.07                                              5.    Benzoic acid         3.36                                               6.    A styrene/allyl alcohol oligomer                                                                   1.12                                                     (RJ-100 Monsanto)                                                                                  69.95                                                    water                6.31                                                                          63.64                                                    glycol               0.08                                                                          63.56                                              7.    Butylated phenolic resin CK-2500                                                                   6.00                                                     (Union Carbide)                                                                                    69.56                                              8.    Trimellitic anhydride                                                                              5.55                                                                          75.11                                                    water                0.10                                                                          75.01                                              9.    Butoxyethanol        12.50                                              10.   Secondary butanol    12.50                                                                         100.01                                             ______________________________________                                    

Reactants 1-6 are charged into a reactor equipped with a heat andcooling source, stirrer, inert gas sparge line, fractionating column,and heated to 480° F. under an inert gas sparge and agitation. Thereactants are held at 480° F. for an acid value of about 7 and aviscosity of about V on the Gardner-Holdt scale when reduced to 75%non-volatile in xylene. The reaction is cooled to about 415° F. and 7 isadded. The reactants are held at 415° F. for about 30 minutes and thencooled to 350° F. Reactant 8 is added and the reaction mixture held at350°-360° F. for an acid value of 42-46 and a viscosity of about Z5 whenreduced to 75 percent non-volatile with equal parts of butoxyethanol andsecondary butanol. The reaction then is cooled to 300° F. Reactant 9 isadded, then reactant 10 is added.

This product is a clear solution having the following physicalproperties:

    ______________________________________                                        Percent non-volatile                                                                              75                                                        Gardner-Holdt viscosity                                                                           Z5                                                        Acid value          45                                                        Gardner color        8                                                        ______________________________________                                    

EXAMPLE 5

    ______________________________________                                                                  PARTS BY                                            REACTANT                  WEIGHT                                              ______________________________________                                        1.  A refined tall fatty acid (Pamolyn                                                                      24.64                                               327B Hercules)                                                            2.  Trimethylolpropane        12.52                                           3.  Neopentyl glycol          8.24                                            4.  Isophthalic acid          20.07                                           5.  Benzoic acid              3.36                                            6.  Styrene/allyl alcohol oligomer                                                                          1.12                                                (RJ-100 Monsanto)                                                                                       69.95                                               water                     6.31                                                                          63.64                                               glycol                    0.08                                                                          63.56                                           7.  Butylated phenolic resin CK-2400                                                                        6.00                                                (Union Carbide, softening paint 290°-315° F.)                                             69.56                                           8.  Trimellitic anhydride     5.55                                                                          75.11                                               water                     0.10                                                                          75.01                                           9.  Butoxyethanol             12.50                                           10. Secondary butanol         12.50                                                                         100.01                                          ______________________________________                                    

The reactants were mixed and reacted as described in Example 4.

This product is a clear solution having the following physicalproperties.

    ______________________________________                                        Percent non-volatile                                                                              75                                                        Gardner-Holdt viscosity                                                                           Z5                                                        Acid value          44                                                        Gardner color        9                                                        ______________________________________                                    

The performance of the resins of Examples 1 and 3 were compared bycompounding a coating composition with pigments, pigment extenders,thickeners, defoamers, surfactants and anti-skimming agents and otheradditives that was a low gloss black enamel with the binders of Examples1 and 3 at 75% non-volatiles and additives as identified below.

PIGMENT GRIND

    ______________________________________                                                              PARTS BY                                                                      WEIGHT                                                  ______________________________________                                        INGREDIENTS                                                                   WATER REDUCIBLE RESIN (75% N.V.)                                                                      9.08                                                  Ammonium Hydroxide-28%  0.62                                                  Sec-Butanol             1.56                                                  Special Black 4 (Degussa) - pigment                                                                   1.56                                                  Aerosil R-972 (Degussa) - thickner                                                                    0.52                                                  Imsil A-10 (Illinois Mineral)-pigment                                                                 3.75                                                  extender                                                                      VP-020 (Byk-Mallinckrodt) - defoamer                                                                  0.31                                                  Surfynol 104E (Air Products) - surfactant                                                             0.20                                                  Deionized Water         10.38                                                 Pebblemill to 7.5 N.S.                                                        GRIND LET DOWN                                                                WATER REDUCIBLE RESIN (75% N.V.)                                                                      26.99                                                 Ammonium Hydroxide-28%  1.27                                                  6% Cobalt Intercar (Interstab)-drier                                                                  0.27                                                  6% Zirco Intercar (Interstab)-drier                                                                   0.36                                                  4% Calcium Intercar (Interstab)-drier                                                                 0.20                                                  Sec-Butanol             1.56                                                  Active-8 (R. T. Vanderbilt)-an activator                                                              0.09                                                  to increase effectiveness of metal                                            driers                                                                        Exkin #2 (Tenneco) - antiskinning agent                                                               0.09                                                  to retard oxidative reactions                                                 during storage                                                                Deionized Water         35.55                                                 Deionized Water (Hold for Viscosity                                                                   5.61                                                  Adjustment) Totals      99.97                                                 Totals                                                                        ENAMEL PROPERTIES                                                             % Non-Volatiles                                                               (By Weight):            33.44                                                 (By Volume):            28.43                                                 Pigment/Binder Weight Ratio:                                                                          0.21                                                  Solvent VOC:            2.54 lbs/gallon                                                               304.28 gms/liter                                      Viscosity               60-80 Sec. #4                                                                 Ford Cup                                              pH                      8.0-8.5                                               ______________________________________                                    

DISPERSION PROCEDURE

The above ingredients are mixed by first mixing all of the pigment grindcomponents except the deionized water. After the latter pigment grindcomponents are completely mixed, the viscosity of the mix is adjusted to65-70 Kreb units using the withheld deionized water. This pigment grindmixture is put into a steel ball mill and ground to a N. S. grind of 7.5on the Hegman scale.

The secondary butanol, metal driers and Active-8 components of the grindlet-down are premixed. This premix and the remainder of the componentsof the grind let-down are mixed in the order shown with the water beingwithheld for the final viscosity adjustment. The grind let-down is mixedinto the grind. The viscosity of the grind and grind let-down mix isadjusted to 60-80 seconds #4 Ford Cup with the withheld water from thelet-down charge.

    ______________________________________                                                        Film Using  Film Using                                                        the Resin of                                                                              the Resin of                                      FILM PROPERTIES Example 1   Example 3                                         ______________________________________                                        Pencil Hardness B           HB                                                Conical Mandrel Pass        Pass                                              QCT Humidity    Dense - Very                                                                              Dense -                                           Resistance      small       medium                                            (115 Hrs.)      blisters    blisters                                          Salt Fog Resistance                                                           (240 Hrs.)                                                                    Scribe Creep (inch)         3/16                                              Surface Blistering                                                                            None        Some very                                                                     small                                                                         blisters                                          ______________________________________                                    

The performance of the resins of Examples 2 and 3 were compared bycompounding a coating composition that was a red oxide primer with thebinders of Examples 2 and 3 at 75% non-volatiles, the pigments andsolvents as identified below.

PIGMENT GRIND

    ______________________________________                                                               PARTS BY                                                                      WEIGHT                                                 ______________________________________                                        COMPONENTS                                                                    Alkyd Resin at 75% N.V.  17.05                                                Butoxyethanol            4.23                                                 BYC (BYC - Mallinckrodt)-a polysiloxane                                                                0.16                                                 copolymer flow agent                                                          Ammonium Hydroxide - 28% Aqueous                                                                       1.06                                                 Deionized Water          17.69                                                Atomite (Thompson-Weinman) - extender                                                                  8.22                                                 pigment                                                                       VVF Barytes (Pfizer) - extender                                                                        8.73                                                 pigment                                                                       Imsil A-10 (Illinois Minerals)                                                                         1.86                                                 Mapico Crimson Red #98 - pigment                                                                       8.52                                                 (Cities Service)                                                              Zinc Phosphate #317 - anti-corrosive                                                                   6.78                                                 pigment (Reichard-Coulston)                                                   Aerosil R-972 (Degussa)  0.79                                                 GRIND LET DOWN                                                                Alkyd Resin at 75% N.V.  6.98                                                 Ammonium Hydroxide - 28% Aqueous                                                                       0.42                                                 Butoxyethanol            1.41                                                 6% Cobalt Intercar (Interstab)                                                                         0.17                                                 4% Calcium Intercar (Interstab)                                                                        1.02                                                 3% Zirconium Intercar (Interstab)                                                                      0.20                                                 Active-8 (R. T. Vanderbilt)                                                                            0.08                                                 Exkin #2 (Tenneco)       0.09                                                 Deionized Water          10.43                                                Deionized Water          4.32                                                                          100.01                                               ENAMEL PROPERTIES                                                             Percent non-volatile     54                                                   Pigment to binder ratio  1.9                                                  Volatile organic components                                                                            2.4                                                  Viscosity (Kreb units)   60-80                                                pH                       8.0-8.5                                              ______________________________________                                    

DISPERSION PROCEDURE

Charge the components of the pigment grind to a pebblemill and grind toa N.S. Grind (Hegman) of 7.5.

Premix the butoxyethanol, metal driers and Activ 8 components of thegrind let-down.

Add all but the last let-down components and the above premix in theorder shown and mix well by stirring.

Adjust the pH to 8.0-8.5 with additional ammonium hydroxide.

Adjust the viscosity to 75 to 80 Kreb units using the remainingcomponent (water).

FILM PREPARATION

The primers are sprayed onto cold-rolled steel Parker test panels toobtain a 1 mil thickness of dry film.

The coated panels are permitted to dry for seven days before evaluation.

    ______________________________________                                        FILM PROPERTIES   Example 2  Example 3                                        ______________________________________                                        Resistance to Lifting                                                                           Excellent  Good                                             Pencil Hardness   HB         HB                                               Impact Resistance (inch-lbs)                                                  Forward           80         30                                               Reverse           10         <5                                               QCT Humidity Resistance                                                                         Very few - Dense - Small                                    (72 Hrs.)         Very small blisters                                                           blisters                                                    Salt Fog Resistance (72 Hrs.)                                                 (Corrosion Resistance)                                                        Scribe Creep (inch)                                                                             1/16       1/4                                              Surface Blistering                                                                              None       Slight                                           Water Soak (12 days)                                                                            No         Moderate                                                           blistering -                                                                             blistering -                                                       slight     considerable                                                       fading     fading                                           Gloss (60/20 degree)                                                                            92/63      92/63                                            ______________________________________                                    

The alkyd resins of Examples 4 and 5 were evaluated in red oxide primersprepared from the following formulation:

PIGMENT GRIND

    ______________________________________                                                               PARTS BY                                                                      WEIGHT                                                 ______________________________________                                        INGREDIENTS                                                                   Phenolic modified alkyd resin at                                                                       12.55                                                75% non-volatile                                                              Butoxyethanol            3.30                                                 BYC 301                  0.12                                                 Ammonia hydroxide (28% aqueous)                                                                        0.83                                                 Atomite                  6.41                                                 Sparmite - BaSO.sub.4 -an extender                                                                     6.80                                                 pigment from Pfizer                                                           Imsil A-10               1.44                                                 Mapico Medium 516 (Columbian Chemical)                                                                 6.61                                                 Zinc Phosphate 317       5.28                                                 Aerosil R-972            0.62                                                 Deionized water          26.73                                                GRIND LET DOWN                                                                Phenolic modified alkyd resin at                                                                       6.17                                                 75% non-volatile                                                              Ammonium hydroxide (28% aqueous)                                                                       0.49                                                 Butoxyethanol            1.10                                                 6% Cobalt Intercar       0.13                                                 4% Calcium Intercar      0.80                                                 6% Zinconium Intercar    0.15                                                 Active-8                 0.07                                                 Exkin #2                 0.08                                                 Deionized water          9.85                                                 Deionized water          10.48                                                                         100.00                                               ______________________________________                                    

These enamels were prepared by the process described as to the primersprepared from the resins of Examples 1 to 3.

The enamels have the following physical properties.

    ______________________________________                                        PRIMER PERFORMANCE                                                                          Film Using   Film Using                                                       modified Alkyd                                                                             modified Alkyd                                     FILM PROPERTIES                                                                             of Composition 4                                                                           of Composition 5                                   ______________________________________                                        Pencil Hardness                                                                             HB           HB                                                 Resistance to lifting                                                                       Very good    Excellent                                          Impact resistance                                                             Forward       40           80                                                 Reverse       <5           30                                                 QCT humidity resist-                                                                        few - very   no blisters                                        ance (144 hrs.)                                                                             small blisters                                                  Salt Fog resistance                                                           (144 Hrs.)                                                                    Scribe Creep (inch)                                                                         1/8          1/8                                                Surface Blistering                                                                          None         None                                               ______________________________________                                    

It should be understood that while certain preferred embodiments of thepresent invention have been illustrated and described, variousmodifications thereof will become apparent to those skilled in the art.Accordingly, the scope of the present invention should be defined by theappended claims and equivalents thereof.

Various features of the invention are set forth in the following claims.

What is claimed is:
 1. A water reducible alkyd resin free of aminoplastsor amino cross-linking agents comprising:a resin which is a reactionproduct of from about 15 to about 50 parts by weight based per 100weight of the resulting water reducible alkyd of a dibasic acid or anacid anhydride thereof, from about 20 to about 50 parts by weight per100 weight of resulting alkyd of a polyol containing at least twohydroxyl groups per molecule, from about 15 to about 60 parts by weightper 100 weight of resulting alkyd of a monobasic carboxylic acid, fromabout 3 to about 15 parts by weight per 100 weight of resulting alkyd ofa tricarboxylic acid or acid anhydride thereof, and from about 4 toabout 20 parts by weight per 100 weight of resulting alkyd of analkylated phenolic resin which is not heat reactive to provide a waterreducible alkyd resin which is free of aminoplasts or aminocross-linking agents and curable without said agents.
 2. An alkyd resinas recited in claim 1 wherein the alkylated phenolic resin has alkylsubstitution at the para position on at least one of the aromatic ringsof the phenolic resin and the alkyl groups are straight or branchedhaving from 1 to 18 carbon atoms.
 3. An alkyd resin as recited in claim2 wherein the alkylated phenolic resin is a reaction product of analkylated phenol and formaldehyde under acid conditions.
 4. An alkydresin as recited in claim 1 wherein the dibasic acid or anhydridethereof, the polyol and the fatty acid are reacted to form an alkyd, thealkylated phenolic resin is mixed with the alkyd to form a phenolicalkyd mix and the tricarboxylic acid or anhydride thereof is reactedwith the phenolic alkyd mix to form the water reducible alkyd resin. 5.An alkyd resin as recited in claim 2 wherein the dibasic acid oranhydride thereof, the polyol and the monobasic carboxylic acid arereacted to form an alkyd, this alkylated phenolic resin is mixed withthe alkyd to form a phenolic alkyd mix and the tricarboxylic acid oranhydride thereof is reacted with the phenolic alkyd mix to form thewater reducible alkyd resin.
 6. An alkyd resin as recited in claim 3wherein the dibasic acid or anhydride thereof, the polyol and themonobasic carboxylic acid are reacted to form an alkyd, the alkylatedphenolic resin is mixed with the alkyd to form a phenolic alkyd mix andthe tricarboxylic acid or anhydride thereof is reacted with the phenolicalkyd mix to form the water reducible alkyd resin.
 7. An alkyd resin asrecited in claim 1 wherein the dibasic acid or anhydride thereof isisophthalic acid or the anhydride thereof, terephthalic acid or theanhydride thereof, phthalic acid or the anhydride thereof, or mixturesthereof, the polyol is neopentyl glycol, propylene glycol, trimethylolpropane or mixtures thereof, and the tricarboxylic acid or anhydridethereof is trimellitic acid or the anhydride thereof.
 8. An alkyd resinas recited in claim 2 wherein the dibasic acid or anhydride thereof isisophthalic acid or the anhydride thereof, terephthalic acid or theanhydride thereof, phthalic acid or the anhydride thereof, or mixturesthereof, the polyol is neopentyl glycol, propylene glycol, trimethyolpropane or mixtures thereof, and the tricarboxylic acid or anhydridethereof is trimelletic acid or the anhydride thereof.
 9. An alkyd resinas recited in claim 4 wherein the dibasic acid or anhydride thereof isisophthalic acid or the anhydride thereof, terephthalic acid or theanhydride thereof, phthalic acid or the anhydride thereof, or mixturesthereof, the polyol is neopentyl glycol, propylene glycol, trimethyolpropane or mixtures thereof, and the tricarboxylic acid or anhydridethereof is trimelletic acid or the anhydride thereof.
 10. An alkyd resinas recited in claim 5 wherein the dibasic acid or anhydride thereof isisophthalic acid or the anhydride thereof, terephthalic acid or theanhydride thereof, phthalic acid or the anhydride thereof, or mixturesthereof, the polyol is neopentyl glycol, propylene glycol, trimethyolpropane or mixtures thereof, and the tricarboxylic acid or anhydridethereof is trimelletic acid or the anhydride thereof.
 11. A method ofmaking a water reducible alkyd resin which is free of aminoplasts oramino cross-linking agents, said method comprising:mixing reactantscomprising from about 15 to about 60 parts by weight per 100 weight ofresulting water reducible alkyd resin of a monobasic carboxylic acid,from about 20 to about 50 parts by weight per 100 weight of resultingwater reducible alkyd resin of a polyol having at least two hydroxylgroups, from about 15 to about 50 parts by weight based per 100 weightof the resulting water reducible alkyd resin of a dibasic acid or anacid anhydride thereof; mixing from about 4 to about 20 parts by weightper 100 weight of resulting water reducible alkyd resin of an alkylatedphenolic resin which is not heat reactive into the reactants, thereactants and the alkylated phenolic forming a reactant phenolic resinmix; heating the reactant phenolic resin mix to form a phenolic alkydmix; and reacting said phenolic alkyd mix with from about 3 to about 15parts by weight per 100 weight of resulting water reducible alkyd resinof a tricarboxylic acid or an acid anhydride thereof to form the waterreducible alkyd resin which is free of aminoplasts or aminocross-linking agents and is curable without said agents. reacting saidphenolic alkyd mix with from about 4 to about 20 parts by weight per 100weight of resulting alkyd of a tricarboxylic
 12. A method as recited inclaim 11 wherein the alkylated phenolic resin has alkyl substitution atthe para position on at least one of the aromatic rings of the phenolicresin and the alkyl groups are straight or branched having from 1 to 18carbon atoms.
 13. A method as recited in claim 12 wherein the alkylatedphenolic resin is a reaction product of any alkylated phenol andformaldehyde under acid conditions.
 14. A method as recited in claim 11wherein the dibasic acid or anhydride thereof, the polyol and themonobasic carboxylic acid are reacted to form an alkyd, the alkylatedphenolic resin is mixed with the alkyd to form a phenolic alkyd mix andthe tricarboxylic acid or anhydride thereof is reacted with the phenolicalkyd mix to form the water reducible alkyd resin.
 15. A method asrecited in claim 12 wherein the dibasic acid or anhydride thereof, thepolyol and the monobasic carboxylic acid are reacted to form an alkyd,the alkylated phenolic resin is mixed with the alkyd to form a phenolicalkyd mix and the tricarboxylic acid or anhydride thereof is reactedwith the phenolic alkyd mix to form the water reducible alkyd resin. 16.A method as recited in claim 13 wherein the dibasic acid or anhydridethereof, the polyol and the monobasic carboxylic acid are reacted toform an alkyd, the alkylated phenolic alkyd mix and the tricarboxylicacid or anhydride thereof is reacted with the phenolic alkyd mix to formthe water reducible alkyd resin.
 17. A method as recited in claim 11wherein the dibasic acid or anhydride thereof is isophthalic acid of theanhydride thereof, terephthalic acid or the anhydride thereof, phthalicacid or the anhydride thereof, or mixtures thereof, the polyol isneopentyl glycol, propylene glycol, trimethyol propane or mixturesthereof, and the tricarboxylic acid or anhydride thereof is trimelliticacid or the anhydride thereof.
 18. A method as recited in claim 12wherein the dibasic acid or anhydride thereof is isophthalic acid or theanhydride thereof, terephthalic acid or the anhydride thereof, phthalicacid or the anhydride thereof, or mixtures thereof, the polyol isneopentyl glycol, propylene glycol, trimethyol propane or mixturesthereof, and the dricarboxylic acid or anhydride thereof is trimelliticacid or the anhydride thereof.
 19. A method as recited in claim 14wherein the dibasic acid or anhydride thereof is isophthalic acid or theanhydride thereof, terephthalic acid or the anhydride thereof, phthalicacid or the anhydride thereof, or mixtures thereof, the polyol isneopentyl glycol, propylene glycol, trimethyol propane or mixturesthereof, and the tricarboxylic acid or anhydride thereof is trimelliticacid or the anhydride thereof.
 20. A method as recited in claim 15wherein the dibasic acid or anhydride thereof is isophthalic acid or theanhydride thereof, terephthalic acid or the ahydride thereof, phthalicacid or the anhydride thereof, or mixtures thereof, the polyol isneopentyl glycol, propylene glycol, trimethyol propane or mixturesthereof, and the tricarboxylic acid or anhydride thereof is trimelliticacid or the ahydride thereof.
 21. A method as recited in claim 14wherein the polyol and the monobasic carboxylic acid are reacted to forman ester and the ester is reacted with the dibasic acid to form analkyd.
 22. A method as recited in claim 16 wherein the polyol and themonobasic carboxylic acid are reacted to form an ester and the ester isreacted with the dibasic acid to form an alkyd.
 23. A method as recitedin claim 20 wherein the polyol and the monobasic carboxylic acid arereacted to form an ester and the ester is reacted with the dibasic acidto form an alkyd.
 24. A resin made according to the method of claim 11.25. A resin made according to the method of claim
 12. 26. A resin madeaccording to the method of claim
 14. 27. A resin made according to themethod of claim
 20. 28. A resin made according to the method of claim23.